EP0714414B1 - Procede de preparation de composes vinyle polymerisables par voie anionique - Google Patents

Procede de preparation de composes vinyle polymerisables par voie anionique Download PDF

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Publication number
EP0714414B1
EP0714414B1 EP94924853A EP94924853A EP0714414B1 EP 0714414 B1 EP0714414 B1 EP 0714414B1 EP 94924853 A EP94924853 A EP 94924853A EP 94924853 A EP94924853 A EP 94924853A EP 0714414 B1 EP0714414 B1 EP 0714414B1
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EP
European Patent Office
Prior art keywords
styrene
flow tube
initiator
reaction
reaction zone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP94924853A
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German (de)
English (en)
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EP0714414A1 (fr
Inventor
Franz Brandstetter
Hermann Gausepohl
Reiner Thiele
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BASF SE
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BASF SE
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Publication date
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/06—Organic solvent

Definitions

  • the invention relates to a process for the polymerization of a anionically polymerizable compound, especially for Manufacture of crystal clear polystyrene or polybutadiene.
  • U.S. Patent 4,883,846 discloses a method for anionic polymerization of styrene. After that Styrene in ethylbenzene with n-butyllithium in one reactor adiabatic, i.e. polymerized without heat dissipation.
  • the object of the invention was to overcome the disadvantages described avoid and an economical process for producing e.g. crystal clear polystyrene or polybutadiene through anionic Specify polymerization.
  • the task is solved by a continuous process for anionic polymerization of (co) polymerizable vinyl or Diene compounds selected from styrene, ⁇ -methylstyrene, Vinyl toluene, tert-butyl styrene and butadiene in solution and in a reaction zone designed as a flow tube, which does not contains moving parts, using an organometallic Initiator, in which the implementation in the invention essentially adiabatic, i.e. without heat exchange with the Environment and a pressure is selected that is sufficient to avoid premature boiling of the mixture and a to achieve sufficient throughput speed and Residence time is less than 5 minutes.
  • Solvents are used. Suitable are e.g. aliphatic, cycloaliphatic or aromatic Hydrocarbons that are liquid under reaction conditions and preferably contain 4 to 12 carbon atoms. Examples for this are pentane, cyclohexane, methylcyclohexane, toluene, Ethylbenzene or xylene.
  • initiators are, for example, lithium hydrocarbons such as methyl lithium, ethyl lithium, n- or sec-butyllithium, Isopropyllithium, cyclohexyllithium or phenyllithium used. N-Butyl or sec-butyllithium are particularly preferred.
  • the polymerization runs under that for the anionic From typical conditions, i.e. under air and Exclusion of moisture at a temperature between 20 and 200 ° C, preferably between 30 and 180 ° C.
  • the molecular weight is about the molar ratio of initiator and monomers set.
  • the polymerization is generally up to a turnover of over 99.9% guided.
  • the Reaction zone consists of a flow tube in which a Plug flow forms.
  • the flow tube can be static Mixers included to promote axial mixing. So-called Kenics mixers or SMX mixers from the company Sulzer.
  • Kenics mixers or SMX mixers from the company Sulzer.
  • At the entrance (head) of the plug flow reactor there is a Mixture of cleaned and e.g. over alumina dried solvent and distilled monomer compound fed.
  • the initiator solution is metered in separately in order to to avoid an early reaction.
  • the final temperature of the polymer solution is by concentration of the monomers in the starting solution and is so controlled that the thermal termination of the living chain ends is minimal. To reduce this cancellation, you can use the provide a cooling jacket in the last part of the pipe.
  • the reaction is carried out under a pressure high enough is to avoid premature boiling of the mixture and to to achieve a sufficient throughput speed. This is i.a. at a pressure of more than 5, preferably more than 20 cash the case.
  • the method according to the invention works with very high Space-time yield and delivers products with tighter Molecular weight distribution.
  • the molecular weight distribution of the The resulting polymers can be divided by dividing the Amount of initiator and addition of the individual portions to two or controlled more different locations of the flow tube, i.e. can be set wider. So you can use both products wider than those with bimodal or multimodal distribution receive.
  • the living Chain ends with a proton-active substance, for example an alcohol, an acid or a mixture of carbon dioxide and water broken off.
  • a proton-active substance for example an alcohol, an acid or a mixture of carbon dioxide and water broken off.
  • the polymer solution is after known method freed from low molecular weight components and provided with lubricants, antioxidants etc. if necessary.
  • a so-called flash degassing is preferred, the under Pressurized, high-temperature polymer solution in a degasser relaxed and then the pre-degassed melt on one Extruder freed of the remaining solvent.
  • a solution of styrene in ethylbenzene was fed at a rate of 750 l / min.
  • the concentration of styrene was 32.5%.
  • a 1.4 ⁇ 10 -3 molar sec-butyllithium solution in ethylbenzene was fed in separately at the same point.
  • the temperature rose from 40 to 171 ° C. in the course of 100 seconds.
  • the turnover was 100%.
  • the space-time yield was 9360 kg / m 3 h.
  • Example 1 was repeated with the proviso that the initiators split in a 1: 1 ratio and the first half at the entrance of the Reactor and the second half in the middle (i.e. after 20 m Pipe length) was fed.
  • the space-time yield was 8430 kg / m 3 h.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Polymerization Catalysts (AREA)

Abstract

L'invention concerne un procédé continu de polymérisation de composés vinyle ou diène (co)polymérisables par voie anionique, en solution et dans une zone de réaction se présentant sous forme de tuyau d'écoulement, à l'aide d'un initiateur organométallique. La réaction s'effectue sensiblement sans échange de chaleur avec l'environnement. Le temps de séjour est inférieur à 5 minutes et la zone de réaction ne contient pas de partie en mouvement.

Claims (5)

  1. Procédé en continu pour la polymérisation anionique de composés vinyliques respectivement diéniques (co)polymérisables choisis parmi le styrène, l'α-méthylstyrène, le vinyltoluène, le tert.-butylstyrène et le butadiène en solution et dans une zone réactionnelle réalisée sous forme d'un tube d'écoulement qui ne contient pas d'éléments mobiles, en utilisant un initiateur organométallique, caractérisé en ce qu'on procède à la mise en réaction dans des conditions essentiellement adiabatiques, c'est-à-dire sans échange thermique avec l'environnement et on sélectionne une pression qui suffit pour empêcher une ébullition prématurée du mélange et pour atteindre une vitesse de passage suffisante, le temps de séjour étant inférieur à 5 minutes.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on met en oeuvre le styrène à titre de composé vinylique.
  3. Procédé selon la revendication 1, caractérisé en ce qu'on met en oeuvre le n- ou le sec.-butyllithium à titre d'initiateur.
  4. Procédé selon la revendication 1, caractérisé en ce qu'on met en oeuvre, à titre de solvant, le cyclohexane, le méthylcyclohexane ou l'éthylbenzène.
  5. Procédé selon la revendication 1, caractérisé en ce que le tube d'écoulement contient au moins en partie des mélangeurs statiques.
EP94924853A 1993-08-16 1994-08-08 Procede de preparation de composes vinyle polymerisables par voie anionique Expired - Lifetime EP0714414B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4327495 1993-08-16
DE4327495A DE4327495A1 (de) 1993-08-16 1993-08-16 Verfahren zur Herstellung von anionisch polymerisierbaren Vinylverbindungen
PCT/EP1994/002620 WO1995005401A2 (fr) 1993-08-16 1994-08-08 Procede de preparation de composes vinyle polymerisables par voie anionique

Publications (2)

Publication Number Publication Date
EP0714414A1 EP0714414A1 (fr) 1996-06-05
EP0714414B1 true EP0714414B1 (fr) 1998-05-20

Family

ID=6495302

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Application Number Title Priority Date Filing Date
EP94924853A Expired - Lifetime EP0714414B1 (fr) 1993-08-16 1994-08-08 Procede de preparation de composes vinyle polymerisables par voie anionique

Country Status (5)

Country Link
EP (1) EP0714414B1 (fr)
JP (1) JPH09501709A (fr)
DE (2) DE4327495A1 (fr)
ES (1) ES2116611T3 (fr)
WO (1) WO1995005401A2 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014075901A1 (fr) * 2012-11-15 2014-05-22 Evonik Oil Additives Gmbh Procédé de production de polybutadiène

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3356763A (en) * 1962-04-09 1967-12-05 Phillips Petroleum Co Continuous process for producing block copolymers of dienes and vinyl aromatic hydrocarbons
US4200713A (en) * 1977-05-04 1980-04-29 Bayer Aktiengesellschaft Process for the anionic homo- or co-polymerization of aromatic vinyl compounds
US4965327A (en) * 1989-10-23 1990-10-23 The Goodyear Tire & Rubber Company Synthesis of polydiene rubber by high solids solution polymerization
EP0522641B1 (fr) * 1991-07-04 1996-10-16 Shell Internationale Researchmaatschappij B.V. Polymérisation anionique dans une extrudeuse

Also Published As

Publication number Publication date
ES2116611T3 (es) 1998-07-16
WO1995005401A2 (fr) 1995-02-23
JPH09501709A (ja) 1997-02-18
EP0714414A1 (fr) 1996-06-05
WO1995005401A3 (fr) 1995-03-23
DE4327495A1 (de) 1995-02-23
DE59406039D1 (de) 1998-06-25

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